CN113274296A - Photo-curing temperature-sensitive color-changing adhesive, adhesive composition, preparation and application thereof - Google Patents
Photo-curing temperature-sensitive color-changing adhesive, adhesive composition, preparation and application thereof Download PDFInfo
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- CN113274296A CN113274296A CN202110574616.XA CN202110574616A CN113274296A CN 113274296 A CN113274296 A CN 113274296A CN 202110574616 A CN202110574616 A CN 202110574616A CN 113274296 A CN113274296 A CN 113274296A
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/30—Compositions for temporarily or permanently fixing teeth or palates, e.g. primers for dental adhesives
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
- A61K6/884—Preparations for artificial teeth, for filling teeth or for capping teeth comprising natural or synthetic resins
- A61K6/891—Compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- A61K6/893—Polyurethanes
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/15—Compositions characterised by their physical properties
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/60—Preparations for dentistry comprising organic or organo-metallic additives
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/60—Preparations for dentistry comprising organic or organo-metallic additives
- A61K6/62—Photochemical radical initiators
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/60—Preparations for dentistry comprising organic or organo-metallic additives
- A61K6/65—Dyes
- A61K6/68—Thermochromic dyes
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
- C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
- C08F222/106—Esters of polycondensation macromers
- C08F222/1065—Esters of polycondensation macromers of alcohol terminated (poly)urethanes, e.g. urethane(meth)acrylates
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
- C08F290/067—Polyurethanes; Polyureas
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/05—Alcohols; Metal alcoholates
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/101—Esters; Ether-esters of monocarboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/11—Esters; Ether-esters of acyclic polycarboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/17—Amines; Quaternary ammonium compounds
- C08K5/18—Amines; Quaternary ammonium compounds with aromatically bound amino groups
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
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- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
- C09J175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
- C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
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- C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
Abstract
The invention discloses a photo-curing temperature-sensitive color-changing adhesive, an adhesive composition, and preparation and application thereof, wherein the adhesive consists of the following components: 10-20wt% of acrylic polyurethane, 10-20wt% of Bis-GMA, 10-20wt% of triethylene glycol dimethacrylate, 10-20wt% of ethoxylated trimethylolpropane triacrylate, 10-20wt% of HEMA, 10-20wt% of modified silicon dioxide, 1-5wt% of a light-induced component, 1-5wt% of BHT, 1-5wt% of KH 5701-5 wt% and 1-2wt% of a temperature-sensitive color-changing component. The adhesive has the characteristics of in vitro color development and no color in an oral environment, and can help doctors to remove residues on tooth surfaces more conveniently when bonding and removing brackets.
Description
Technical Field
The invention relates to the technical field of adhesives, in particular to the technical field of a photocuring temperature-sensitive color-changing adhesive for orthodontics.
Background
Orthodontics is mainly used for studying the etiology and mechanism of malocclusion and malformation, diagnosis and analysis, and prevention and treatment thereof. Orthodontic treatment is mainly to adjust the coordination among nerves and muscles of facial bones, teeth and maxillofacial parts, that is, to adjust abnormal relationships among maxilla and mandible, between upper and lower teeth, between teeth and jawbone, and between nerves and muscles connecting them, by various orthodontic devices, with the ultimate aim of correction being to achieve balance, stability and beauty of the oromandibular system.
The bonding system of brackets for orthodontics is generally a three-component system comprising an acid etching agent, a pretreating agent and an adhesive, wherein the existing orthodontic adhesives on the market are mainly light-cured and two-component resin materials.
In order to meet the increasing aesthetic requirements, orthodontic adhesives are often designed to be close to the color of teeth, but the clinical use of the orthodontic adhesives by doctors is difficult to distinguish tooth surfaces from the adhesives, so that the operation is difficult when redundant adhesives are removed, the incomplete removal causes residual adhesives on the tooth surfaces, the excessive removal damages the tooth surfaces, and therefore, the position and the residual quantity of the adhesives are shown in a reasonable way.
Although some conventional photo-curing temperature-sensitive color-changing adhesives on the market can also meet the color-changing requirement, most of the conventional photo-curing temperature-sensitive color-changing adhesives cannot simultaneously switch between color and colorlessness, and the adhesives which can rapidly switch color at the temperature close to the oral cavity temperature of a human body and meet the oral application requirement are in urgent need of development. In addition, good stability and effective bonding strength are important for prolonging the service life of orthodontic adhesives based on the long-term use requirement of orthodontic adhesives, and an orthodontic adhesive system having good stability and excellent and proper effective bonding strength is lacked in the prior art.
Disclosure of Invention
In order to overcome the above disadvantages of the prior art, an object of the present invention is to provide a novel photo-curable temperature-sensitive color-changing adhesive which can develop color at a low temperature, becomes colorless when reaching a human oral temperature, and has good adhesiveness, transparency, cohesion and photo-curing rate, and good stability in an oral environment.
The present invention also provides an adhesive composition comprising the photo-curable temperature-sensitive color-changing adhesive and a photo-curable pretreating agent adapted thereto, which has excellent adhesive strength capable of enhancing orthodontic effect, is safe and sanitary, and is easy for oral manipulation.
The invention also aims to provide a preparation method and application of the photo-curing temperature-sensitive color-changing adhesive and the adhesive composition.
The invention firstly provides the following technical scheme:
the photo-curing temperature-sensitive color-changing adhesive comprises the following raw material components in percentage by weight: 20-60wt% of acrylic polyurethane, 5-10wt% of bisphenol A glyceride (Bis-GMA), 10-20wt% of triethylene glycol dimethacrylate, 10-20wt% of ethoxylated trimethylolpropane triacrylate, 10-20wt% of hydroxyethyl methacrylate (HEMA), 1-2wt% of a light-induced component, 0.1-1wt% of Butylated Hydroxytoluene (BHT) and 0.01-2wt% of a temperature-sensitive color-changing component.
The light-induced component refers to a chemical substance and/or a composition thereof with a light-induced effect, and the temperature-sensitive color-changing component refers to a chemical substance and/or a composition thereof with temperature sensitivity and capable of changing color according to different temperatures.
In the adhesive, cyano in acrylic polyurethane provides adhesiveness, prepolymer can provide cohesion and good form for products, long chain can provide flexibility, Bis-GMA can provide better rigidity due to a double benzene ring structure, triethylene glycol dimethacrylate has better fluidity, viscosity of a resin system can be reduced, and the ethylene glycol dimethacrylate has a crucial influence on the mixing amount of subsequent fillers, and fatty chain of the ethylene glycol dimethacrylate can also provide toughness; the ethoxylated trimethylolpropane triacrylate not only provides fluidity, but also can provide higher crosslinking degree after being cooperated with other components due to the characteristics of three functional groups; HEMA, in addition to providing fluidity, can also make the product more viscous and reduce the contact angle with the tooth surface; the photoinitiation component not only provides proper photoinitiation capability for the product, but also can keep the product with good transparency and optimal curing rate by matching with other components under proper dosage; BHT can be matched with other components under a proper amount of content to stabilize the polymerization process, and the obtained product achieves ideal mechanical and optical properties; the temperature-sensitive color-changing component can provide a temperature-sensitive color-changing effect, and can eliminate the stress concentration of the product after being cooperated with other components under proper content and selection, so that the stress of the product is uniform, and the biological safety of the product is improved; the components have synergistic effect at proper content, so that the adhesive has good toughness, rigidity and strength, good fluidity and bonding force with tooth surfaces, good biocompatibility and stress uniformity.
According to some preferred embodiments of the present invention, the acrylic polyurethane has a molecular weight of 1000-.
According to some preferred embodiments of the present invention, the temperature-sensitive color-changing component is selected from one or more of a temperature-sensitive dye and/or a complex thereof, a polythiophene thermochromic pigment, a liquid crystal derivative of cholesterol.
According to some preferred embodiments of the present invention, the temperature-sensitive dye complex is composed of a pH-sensitive dye, a developer, and a non-volatile hydrophobic solvent.
According to some preferred embodiments of the present invention, the pH sensitive dye is selected from spironolactones, such as one or more of diaryl phthalate, episalvianic acid cryptospiriolide, fluoran.
According to some preferred embodiments of the invention, the developer is selected from proton donor compounds, such as one or more of carboxylic acids, phenols, lewis acids, such as phenol.
According to some preferred embodiments of the present invention, the non-volatile hydrophobic solvent is selected from one or more of fatty acids, amides and alcohols having a melting point of 30-37 ℃, such as cetyl alcohol.
According to some preferred embodiments of the present invention, the liquid crystal derivative of cholesterol is selected from one or more of cholesterol pelargonate, cholesterol oleyl carbonate, cholesterol acetate, cholesterol benzoate, and chlorinated cholesterol.
According to some preferred embodiments of the invention, the photoinitiating component comprises a free radical photoinitiator.
According to some preferred embodiments of the present invention, the photoinitiating component is camphorquinone and/or a hydrogen abstraction type photoinitiator.
According to some preferred embodiments of the present invention, the hydrogen abstraction-type photoinitiator is selected from isooctyl p-dimethylaminobenzoate.
According to some preferred embodiments of the invention, the adhesive further comprises a filler, such as one or more of silica, ground glass frit with heavy metal filings, and a prepolymer filler.
According to some preferred embodiments of the invention, the filler is selected from silica having a particle size of 0.015 to 10 μm.
The invention further provides a preparation method of the photo-curing temperature-sensitive color-changing adhesive, which comprises the following steps:
(1) mixing the acrylic polyurethane, Bis-GMA, triethylene glycol dimethacrylate, ethoxylated trimethylolpropane triacrylate and HEMA according to the proportion;
(2) adding BHT and the photoinitiation component into the mixture obtained in the step (1);
(3) and (3) adding the fumed silica and the temperature-sensitive color-changing component into the mixture obtained in the step (2), and stirring until the whole system becomes a plasticine state which is uniformly mixed and slightly sticky, so as to obtain the adhesive.
According to some preferred embodiments of the present invention, the temperature-sensitive color-changing component is composed of a temperature-sensitive dye and/or a complex thereof and/or a liquid crystal derivative of cholesterol, and is prepared into a microcapsule-type composition before the mixture is added in the step (3).
The invention further provides an adhesive composition which comprises any one of the photo-curing temperature-sensitive color-changing adhesives and/or the adhesive prepared by the preparation method, and a photo-curing pretreatment agent.
According to some preferred embodiments of the present invention, the photo-curing pretreatment agent comprises the following raw material components in percentage: 10-20% of bisphenol A glyceride, 20-80% of hydroxyethyl methacrylate, 0.1-2% of the photoinitiating component, 1-5% of 3- (methacryloyloxy) propyltrimethoxysilane and 0.1-5% of ethanol.
According to some preferred embodiments of the present invention, the photo-curing pretreatment agent further comprises a filler.
According to some preferred embodiments of the present invention, in the adhesive composition, the photo-curable temperature-sensitive color-changing adhesive comprises the following raw material components in percentage by weight: 20wt% of acrylic polyurethane, 5.6wt% of bisphenol A glyceride (Bis-GMA), 12wt% of triethylene glycol dimethacrylate, 6.5wt% of ethoxylated trimethylolpropane triacrylate, 18.6wt% of hydroxyethyl methacrylate (HEMA), 0.3wt% of camphorquinone, 1.6wt% of isooctyl p-dimethylaminobenzoate, 0.1wt% of Butylated Hydroxytoluene (BHT) and 0.04wt% of temperature-sensitive color-changing component; the light-cured pretreating agent comprises the following raw material components in percentage by weight: 18.7% of bisphenol A glyceride, 35.6% of hydroxyethyl methacrylate, 0.64% of camphorquinone, 1.32% of isooctyl p-dimethylaminobenzoate, 5% of 3- (methacryloyloxy) propyltrimethoxysilane and 3.7% of ethanol.
According to some preferred embodiments of the present invention, the above-mentioned method for preparing a photo-curing pretreatment agent comprises:
(1) mixing the bisphenol A glyceride, hydroxyethyl methacrylate, 3- (methacryloyloxy) propyl trimethoxy silane and ethanol according to the proportion, and fully stirring;
(2) and (2) adding the light initiation component into the mixture obtained in the step (1), fully stirring again and keeping out of the sun to obtain the light curing pretreating agent.
The invention further provides an application method of the photo-curing temperature-sensitive color-changing adhesive and/or the adhesive composition, which is used for orthodontic repair.
According to some preferred embodiments of the invention, the applying comprises: and (2) coating the adhesive on a metal bracket for orthodontics, uniformly coating the pretreating agent on the tooth surface, placing the bracket on the tooth surface to ensure that the adhesive is attached to the tooth surface, and after the overflowing adhesive is removed, irradiating the bracket for 10-40 seconds by using a medical ultraviolet curing lamp to obtain a bracket sample after photocuring.
The invention has the following beneficial effects:
the adhesive obtained by the invention can rapidly change color at 33 ℃, is colorless at the temperature higher than 33 ℃ and develops color at the temperature lower than 33 ℃.
The adhesive obtained by the invention can develop color at low temperature, and is colorless when reaching the temperature of the oral cavity of a human body, so that the appearance is not influenced when the adhesive is used in the daily orthodontic process, and the adhesive can develop color through cooling when needing to be removed, thereby achieving the purpose of convenient removal.
The bonding composition can be rapidly cured under the irradiation of an LED ultraviolet lamp, the shear strength of about 3MPa can be achieved within about 20s, the bracket can be sufficiently fixed on the tooth surface, the curing time is short, and the operation time of a doctor is greatly shortened.
The shear strength of the bonding composition obtained by the invention is more than 7MPa, the requirement of orthodontic repair strength is met, and the falling probability of brackets is reduced.
The adhesive composition obtained by the present invention can stably maintain excellent adhesive strength in the oral cavity of a human body for a long period of time.
Drawings
FIG. 1 is a shear test device used in example 2 of the present invention.
FIG. 2 is a comparison of sample 1 obtained in example 3 of the present invention before and after discoloration.
FIG. 3 is a comparison of sample 2 obtained in example 3 of the present invention before and after discoloration.
FIG. 4 is a comparison of sample 3 obtained in example 3 of the present invention before and after discoloration.
FIG. 5 is a comparison of sample 4 obtained in example 3 of the present invention before and after discoloration.
FIG. 6 is a graph of the shear strength stability test obtained in example 23 of the present invention.
Detailed Description
The present invention is described in detail below with reference to the following embodiments and the attached drawings, but it should be understood that the embodiments and the attached drawings are only used for the illustrative description of the present invention and do not limit the protection scope of the present invention in any way. All reasonable variations and combinations that fall within the spirit of the invention are intended to be within the scope of the invention.
Example 1
The temperature-sensitive color-changing component is prepared by the following process
Mono, thermo sensitive dye and/or its complex
(1) Mixing heat-sensitive green (CAS:29512-46-7) or heat-sensitive blue (87563-89-1), phenol and hexadecanol according to the mass ratio =1:1:100, then heating until the system is molten, and fully mixing the components in the system molten state;
(2) and (2) cooling the mixture obtained in the step (1) to room temperature, and preparing microcapsules to obtain dark green or dark blue powder.
Di, liquid crystal derivative of cholesterol
(1) Mixing cholesterol pelargonate, cholesterol oleyl carbonate, cholesterol acetate and cholesterol benzoate according to a certain mass ratio, and preparing into microcapsules to obtain green powder.
Example 2
The photo-curing temperature-sensitive color-changing adhesive for orthodontic treatment is prepared by the following steps:
(1) mixing acrylic polyurethane with molecular weight of about 1700, Bis-GMA (bisphenol A glyceride), triethylene glycol dimethacrylate (CAS: 109-16-0), ethoxylated trimethylolpropane triacrylate (CAS: 28961-43-5) and HEMA (hydroxyethyl methacrylate) according to a ratio until the whole system is fully and uniformly mixed;
(2) adding BHT (antioxidant 264) and a photoinitiator combination (mass ratio is 1: 1.5) consisting of camphorquinone and isooctyl p-dimethylaminobenzoate into the mixture obtained in the step (1), and stirring uniformly again;
(3) adding a filler and the temperature-sensitive color-changing component obtained in the embodiment 1 into the mixture obtained in the step (2), stirring until the whole system becomes a plasticine state which is uniformly mixed and slightly sticky, thus obtaining the adhesive, and curing the adhesive for 20s by using a medical ultraviolet curing lamp to realize complete crosslinking and curing;
wherein the specific mass ratio of the raw materials is as follows: 35wt% of acrylic polyurethane, 5wt% of Bis-GMA, 10wt% of triethylene glycol dimethacrylate, 20wt% of ethoxylated trimethylolpropane triacrylate, 10wt% of HEMA, 2wt% of a photoinitiation system, 1wt% of BHT1 and a temperature-sensitive color-changing component, and the balance of fumed silica.
The light-cured pretreating agent is prepared by the following processes:
(1) mixing the bisphenol A glyceride, hydroxyethyl methacrylate, 3- (methacryloyloxy) propyl trimethoxy silane and ethanol according to the proportion, and fully stirring;
(2) and (2) adding the same photo-initiation component used in the preparation of the photo-curing temperature-sensitive color-changing adhesive into the mixture obtained in the step (1), and fully stirring and keeping out of the sun again.
Wherein the specific mass ratio of the raw materials is as follows: 15% of bisphenol A glyceride, 75% of hydroxyethyl methacrylate, 1% of photoinitiation component, 4% of 3- (methacryloyloxy) propyl trimethoxy silane and 5% of ethanol.
The photo-curing temperature-sensitive color-changing adhesive is a solid adhesive with plasticine state and has the characteristic of temperature-sensitive color change; the resulting photocurable pretreatment was a viscous, transparent yellow liquid.
Example 3
Different temperature-sensitive color-changing components were prepared according to the procedure of example 1, and then a photo-curable temperature-sensitive color-changing adhesive for orthodontics was prepared according to the procedure of example 2 to obtain an adhesive cured product as shown in fig. 2 to 5, and color testing was performed thereon, and it was found that sample 1 exhibited dark green color (C100, Y100 color) at a temperature of 22 ℃ or lower, color faded and changed to nearly colorless at a temperature of 22 ℃ or higher, sample 2 exhibited dark blue color (C100, M100 color) at a temperature of 22 ℃ or lower, color faded and changed to nearly colorless at a temperature of 22 ℃ or higher, sample 3 exhibited peacock green color (C60, Y25 color) at a temperature of 33 ℃ or lower, color faded and changed to nearly colorless at a temperature of 33 ℃ or lower, and sample 4 exhibited baby blue color (C100, M60 color) at a temperature or higher, and color faded and changed to nearly colorless at a temperature or higher.
Examples 4 to 6
An adhesive was prepared by the method of example 2, changing only the kind of the temperature-sensitive discoloration component, and the other components were not changed, as shown in the following table:
TABLE 1 measurement of temperature-sensitive Effect in the products of examples 4 to 6
Example 7
The adhesive composition obtained in example 2 was tested for shear strength by the following procedure with the device as shown in figure 1:
taking the front tooth of a bovine tooth, cutting off the tooth root under running water by using a carborundum sheet, cutting into a proper size which can be placed in a tooth cup, embedding the near surface, the far surface and the palatal surface of the dental crown in the tooth cup by using superhard gypsum or self-setting resin, exposing the buccal surface of the dental crown and slightly higher than the edge of the metal cup;
grinding the embedded teeth on a grinding machine, and sequentially grinding the embedded teeth by using abrasive paper with a mesh number from low to high until the tooth surfaces are smooth;
cleaning the tooth surface with alcohol, and drying with oilless gas;
uniformly coating an acid etching agent on the tooth surface, performing acid etching for 20-30s, then flushing the acid etching agent by using high-speed flowing water, and drying the tooth surface by using high-pressure oil-free air;
the adhesive prepared according to the embodiment 1 is uniformly coated on an orthodontic flat-bottom metal bracket, the prepared pretreating agent is uniformly coated on the tooth surface, the bracket is placed on the tooth surface, the adhesive is uniformly pressed by lightly pressing, and then the excessive overflowing adhesive is removed completely.
And (5) irradiating for 20s by using a medical ultraviolet curing lamp, and finishing the mounting of the bracket sample.
The samples prepared by the sample preparation process are tested according to the following processes, the shear bonding strength is tested according to a method for testing the 6.5 bonding strength in the YY/T0269-:
table 2 example 7 sample shear strength
It can be seen that the adhesive for orthodontic use prepared in example 7 had a bonding strength of 3.6 to 7.9MPa after photocuring for 20 seconds.
Examples 8 to 14
The photo-curable temperature-sensitive color-changing adhesive for orthodontic treatment in examples 8 to 14 was prepared by the following procedure:
(1) mixing acrylic polyurethane with the viscosity of 15000-;
(2) adding BHT and a photoinitiator into the mixture obtained in the step (1), and stirring uniformly again;
(3) adding a filler and the temperature-sensitive color-changing component prepared from the temperature-sensitive dye and/or the compound thereof in the embodiment 1 into the mixture obtained in the step (2), stirring until the whole system becomes a plasticine state which is uniformly mixed and slightly sticky, and obtaining the adhesive, wherein the adhesive can be completely crosslinked and cured after being cured for 20s by using a medical ultraviolet curing lamp;
the formula of the photo-curing pretreating agent in the embodiment 2 is adopted, and the proportion of the photo-curing temperature-sensitive binder raw materials in each embodiment is specifically shown in the following table 3:
TABLE 3 example 8-14 raw material ratios
Examples 15 to 21
The preparation of the pretreatment was carried out according to the method of example 2, wherein:
TABLE 4 example 15-21 raw material ratios
Example 22
The binder was used with the pretreatment as in example 7 and tested for shear strength, the results of which are shown in the following table:
TABLE 5 shear Strength test results
It can be seen from the table that the combination of example 18+ example 8 optimizes the strength.
Example 23
50 samples prepared according to the optimum combination of example 22 were placed in artificial saliva and 10 samples were taken every 10 days for shear strength testing according to the method of example 7, the results of which are shown in FIG. 6,
as can be seen from FIG. 6, the shear strength of the optimal combination in example 22 is finally substantially stabilized at around 10MPa, meeting the clinical strength requirements of orthodontic repair.
The above examples are merely preferred embodiments of the present invention, and the scope of the present invention is not limited to the above examples. All technical schemes belonging to the idea of the invention belong to the protection scope of the invention. It should be noted that modifications and embellishments within the scope of the invention may be made by those skilled in the art without departing from the principle of the invention, and such modifications and embellishments should also be considered as within the scope of the invention.
Claims (10)
1. The photo-curing temperature-sensitive color-changing adhesive is characterized in that: the material comprises, by mass, 20-60% of acrylic polyurethane, 5-10% of bisphenol A glyceride, 10-20% of triethylene glycol dimethacrylate, 10-20% of ethoxylated trimethylolpropane triacrylate, 10-20% of hydroxyethyl methacrylate, 1-2% of a photo-initiation component, 0.1-1% of dibutyl hydroxy toluene and 0.01-2% of a temperature-sensitive color-changing component.
2. The adhesive of claim 1, wherein: the temperature-sensitive color-changing component is selected from one or more of temperature-sensitive dyes and/or compounds thereof, polythiophene thermochromic pigments and liquid crystal derivatives of cholesterol.
3. The adhesive of claim 2, wherein: the temperature-sensitive dye compound consists of a pH-sensitive dye, a color-developing agent and a non-volatile hydrophobic solvent, wherein the color-developing agent is selected from one or more of proton donor compounds; the pH sensitive dye is selected from one or more of spironolactone compounds; the non-volatile hydrophobic solvent is selected from one or more of fatty acid, amide and alcohol with melting point of 30-37 deg.C.
4. The adhesive of claim 1, wherein: the photoinitiating component is camphorquinone and/or a hydrogen abstraction type photoinitiator.
5. The adhesive of claim 7, wherein: the hydrogen-extracting photoinitiator is selected from isooctyl p-dimethylaminobenzoate.
6. The adhesive of claim 1, wherein: it also includes a filler selected from one or more of silica, ground glass frit with heavy gold filings, and prepolymer filler.
7. The method of preparing the adhesive according to any one of claims 1-6, comprising:
(1) mixing the acrylic polyurethane, bisphenol A glyceride, triethylene glycol dimethacrylate, ethoxylated trimethylolpropane triacrylate, hydroxyethyl methacrylate and 3- (methacryloyloxy) propyl trimethoxy silane according to the proportion;
(2) adding dibutyl hydroxy toluene and the photoinitiation component into the mixture obtained in the step (1);
(3) and (3) adding the filler and the temperature-sensitive color-changing component into the mixture obtained in the step (2), and stirring until the whole system becomes a plasticine state which is uniformly mixed and slightly sticky, so as to obtain the adhesive.
8. The method of claim 7, wherein: and (4) preparing the temperature-sensitive color-changing component into a microcapsule composition before adding the mixture in the step (3).
9. An adhesive composition characterized by: the photo-curing temperature-sensitive color-changing adhesive comprises the photo-curing temperature-sensitive color-changing adhesive as defined in any one of claims 1-6 and/or the adhesive prepared by the preparation method as defined in claim 7 or 8, and a photo-curing pretreatment agent, wherein the photo-curing pretreatment agent comprises the following raw material components in percentage by weight: 10-20% of bisphenol A glyceride, 20-80% of hydroxyethyl methacrylate, 0.1-2% of the photoinitiating component, 1-5% of 3- (methacryloyloxy) propyltrimethoxysilane and 0.1-5% of ethanol.
10. Use of the adhesive of any one of claims 1-6 and/or the adhesive composition of claim 9 in orthodontics.
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| CN202110574616.XA CN113274296B (en) | 2021-05-25 | 2021-05-25 | Photo-curing temperature-sensitive color-changing adhesive, adhesive composition, preparation and application thereof |
| US17/824,476 US20220282140A1 (en) | 2021-05-25 | 2022-05-25 | Photocurable thermochromic adhesive, adhesive composition and preparation as well as application thereof |
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| CN115120504A (en) * | 2022-07-20 | 2022-09-30 | 武汉大学 | Photochromic orthodontic bracket adhesive and preparation method and application thereof |
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| US20220282140A1 (en) | 2022-09-08 |
| CN113274296B (en) | 2022-02-11 |
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